10-Deacetoxy-7-(triethylsilyl)baccatin III | 149140-51-2

• 分子结构分类: 有机化合物 - 脂质和类脂质分子 - 异戊烯醇脂质
• 英文名称: 10-Deacetoxy-7-(triethylsilyl)baccatin III
• 英文别名: 7-(Triethylsilyl)-10-deoxybaccatin；7-triethylsilyl-10-desacetoxybaccatin III；[(1S,2S,3R,4S,7R,9S,10S,15S)-4-acetyloxy-1,15-dihydroxy-10,14,17,17-tetramethyl-11-oxo-9-triethylsilyloxy-6-oxatetracyclo[11.3.1.03,10.04,7]heptadec-13-en-2-yl] benzoate
• CAS: 149140-51-2
• 化学式: C₃₅H₅₀O₉Si
• 分子量: 642.862
• InChiKey: RUBZGBVXFHKSDM-GQDVWDDGSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.14
• 重原子数：
  45
• 可旋转键数：
  10
• 环数：
  5.0
• sp3杂化的碳原子比例：
  0.69
• 拓扑面积：
  129
• 氢给体数：
  2
• 氢受体数：
  9

反应信息

• 作为反应物：
  描述：

  10-Deacetoxy-7-(triethylsilyl)baccatin III 在 盐酸 、 sodium hydride 作用下， 以 乙腈 为溶剂， 反应 2.5h， 生成 10-Deoxybaccatin 7-xanthate
  参考文献：
  名称：

  The Chemistry of Taxanes: Skeletal Rearrangements of Baccatin Derivatives via Radical Intermediates

  摘要：

  In the course of a synthetic program aimed at systematic defunctionalization of the taxol core for structure activity studies, a number of radical-based deoxygenation reactions were carried out on baccatin III derivatives. In this connection, we have discovered that formation of radicals at positions C-1, C-2, and C-7 in the taxane core of baccatin III results in a number of skeletal rearrangement cascades. Furthermore, the exact composition of the product mixture depends on the specific tin (or silicon) hydride used for the reduction. In the case of C-2- and C-7-derived radicals, direct quenching with tin hydrides without rearrangement was possible under some conditions. However, we were unable to find conditions to quench the C-1 radical, since rearrangement pathways always predominate in this case.

  DOI：

  10.1021/jo00085a040
• 作为产物：
  描述：

  10-脱乙酰基巴卡丁 III 在 咪唑 、 正丁基锂 、 偶氮二异丁腈 、 三正丁基氢锡 作用下， 以 四氢呋喃 、 正己烷 、 N,N-二甲基甲酰胺 、 甲苯 为溶剂， 反应 3.17h， 生成 10-Deacetoxy-7-(triethylsilyl)baccatin III
  参考文献：
  名称：

  The Chemistry of Taxanes: Skeletal Rearrangements of Baccatin Derivatives via Radical Intermediates

  摘要：

  In the course of a synthetic program aimed at systematic defunctionalization of the taxol core for structure activity studies, a number of radical-based deoxygenation reactions were carried out on baccatin III derivatives. In this connection, we have discovered that formation of radicals at positions C-1, C-2, and C-7 in the taxane core of baccatin III results in a number of skeletal rearrangement cascades. Furthermore, the exact composition of the product mixture depends on the specific tin (or silicon) hydride used for the reduction. In the case of C-2- and C-7-derived radicals, direct quenching with tin hydrides without rearrangement was possible under some conditions. However, we were unable to find conditions to quench the C-1 radical, since rearrangement pathways always predominate in this case.

  DOI：

  10.1021/jo00085a040

文献信息

• Process for the preparation of baccatin III analogs bearing new C2 and C4 functional groups
  申请人：Florida State University

  公开号：US06727369B1

  公开（公告）日：2004-04-27

  Process for the preparation of a derivative or analog of baccatin III or 10-desacetyl baccatin III having a C2 substituent other than benzoate and/or a C4 substituent other than acetate in which the C2 benzoate substituent and/or the C4 acetate substituent of a derivative of baccatin III or 10-desacetyl baccatin III is/are selectively reduced to the corresponding hydroxy group(s) and converted to R7COO— and/or R8COO—, respectively, wherein R7 and R8 are independently H, C1-C6 alkyl, C2-C6 alkenyl, C2-C8 alkynyl, moncyclic aryl, or monocyclic heteroaryl.

  这段文字是关于制备紫杉醇前体化合物——特别是baccatin III或10-desacetyl baccatin III的衍生物或类似物——的化学工艺描述。该工艺涉及对baccatin III或10-desacetyl baccatin III的C2位置上的苯甲酸酯基团和/或C4位置上的醋酸酯基团进行选择性还原，将它们转化为相应的羟基，并进一步转化为R7COO—和/或R8COO—，其中R7和R8独立地代表氢、C1-C6烷基、C2-C6烯基、C2-C8炔基、单环芳基或单环杂芳基。以下是中文翻译： 制备baccatin III或10-去乙酰基baccatin III的衍生物或类似物的工艺，该衍生物或类似物具有除苯甲酸酯以外的C2取代基和/或除醋酸酯以外的C4取代基，其中baccatin III或10-去乙酰基baccatin III衍生物的C2位苯甲酸酯取代基和/或C4位醋酸酯取代基被选择性地还原为相应的羟基，并且分别转化为R7COO—和/或R8COO—，其中R7和R8独立地为H，C1-C6烷基，C2-C6烯基，C2-C8炔基，单环芳基或单环杂芳基。
• Studies on the photochemistry of taxol®
  作者：Shi-Hui Chen、Vittorio Farina、Stella Huang、Qi Gao、Jerzy Golik、Terrence W. Doyle

  DOI：10.1016/s0040-4020(01)85337-0

  日期：1994.1

  Irradiation of taxol at 280 nm in a Rayonet reactor yielded a novel pentacyclic derivative containing a new bond between C-3 and C-II. The proposed mechanism involves a triplet intermediate and the first event of the oxa-di-pi-merhane rearrangement. Taxane derivatives that lack both the benzoate at C-2 and the benzamide function at C-3' do not undergo the rearrangement, suggesting the intervention of an intramolecular energy transfer. Irradiation at 300 nm also effects extrusion of the C-9 carbonyl, yielding a ring-contracted product.
• Synthesis of 7-deoxy- and 7,10-dideoxytaxol via radical intermediates
  作者：Shu Hui Chen、Stella Huang、Joydeep Kant、Craig Fairchild、Jianmei Wei、Vittorio Farina

  DOI：10.1021/jo00071a002

  日期：1993.9

  7-Deoxytaxol and 7,10-dideoxytaxol were prepared from baccatin III, employing the Barton deoxygenation procedure and the Holton acylation method at C-13.
• Samarium Diiodide-Mediated Deoxygenation of Taxol: A One-Step Synthesis of 10-Deacetoxytaxol
  作者：Gunda I. Georg、Zacharia S. Cheruvallath

  DOI：10.1021/jo00093a040

  日期：1994.7